Method for producing an organomagnesium complex

ABSTRACT

A method for producing an organomagnesium complex which is soluble in an inert hydrocarbon medium and expressed by the general formula Mg.sub.α Al.sub.β R 1   p  Y q  is provided. In this formula 
     α, β, p and q each is a number greater than zero, 
     α/β = about 0.5 to 20, 
     2α and 3β = p + q, 
     q/β = about 0.5 to 1.5, 
     Y is OR 2  or OSiR 3  R 4  R 5 , 
     R 1 , r 2  and R 3  each independently is a hydrocarbon radical having 1 to 20 carbon atoms, and 
     R 4  and R 5  each independently is a hydrocarbon radical having 1 to 20 carbon atoms, hydrogen or a halogen atom. 
     Said complex is prepared by reacting (A) an organomagnesium compound R 1   a  M g  X 2-a  wherein x is halogen, with (B) an aluminum compound AlYX 2  wherein Y and X have the same meanings as above-defined. This method is superior to the prior art with respect to ease of reaction, high reaction efficiency and safety. Further the complex is safe during storage and handling. When the complex is employed as an olefin polymerization catalyst, the catalyst efficiency is higher and the characteristic properties of the resultant polymer are superior to those of polymers with other complexes.

DESCRIPTION OF THE INVENTION

The present invention relates to a novel method for producing anorganomagnesium complex.

Organomagnesium compounds obtained by reacting an organic halide withmetallic magnesium have been known as so-called Grignard's reagents andwidely used as raw materials for organic syntheses or for catalysts.

Grignard's reagents have been generally prepared using polar compoundssuch as ethers, which, however, are undesirable for some of the uses ofthe reagents. Thus, methods for synthesizing the reagents in an inerthydrocarbon medium have been studied, and methods therefor with a goodefficiency have been proposed (e.g. Brice Smith, Chem. & Ind. p. 1533,1960; Zakharkin, Tetrahedron Letter, p. 631, 1962).

However, since organomagnesium compounds are hardly soluble or insolublein an inert hydrocarbon medium and this is disadvantageous in theirindustrial uses, various attempts have been made to solubilize them. Inone of them, solubilization is effected by forming a complex thereofwith another metallic compound. K. Ziegler obtained a complex MgR₂[AlR'₃ ]₂ by synthesizing a compound RMgCl or R₂ Mg in an ether,removing said ether therefrom and reacting same with AlR'₃ in hexane(Ann. 605, 93-97, 1957). Joh et al obtained a complex MgR₂.AlR'₃(wherein the ratio of Mg : Al is 1 : 1) by reacting MgR₂ with AlR'₃ intoluene or heptane (J. Polymer Sci., A-1, 2503-2522 (1967)).On the otherhand, B. Smith synthesized a complex from a metallic derivative of anorganic compound having a hydroxyl group or an enolizable keto group(e.g. Al(OR)₃) and an organomagnesium compound synthesized in ahydrocarbon, and found that said complex can be substituted fororganolithiums (British Pat. Nos. 1,003,551 (1965) and 955,806 (1964)).According to a tracing experiment carried out by the present inventors,this complex is soluble in a hydrocarbon medium. Further Zakharkinproposed a method for synthesizing an organometal by reacting aGrignard's reagent synthesized in a hydrocarbon medium with a metalhalide (Proceeding of the Academy Science of USSR, 144, 543-545, 1962)).According to a tracing experiment carried out by the present inventors,it has been observed that when AlCl₃ is used for the metal halide, acomplex [MgR₂ ]₆.AlR₃ is formed in the system. Recently two methods forpreparing a solution of dialkylmagnesium using the abovementionedreaction system have been proposed. Namely, according to the method ofJapanese Patent Publication No. 24009/1972, dialkylmagnesium issolubilized by reacting an organomagnesium compound synthesized in ahydrocarbon medium with an organoaluminum compound expressed by ageneral formula AlR_(m) X_(3-m) wherein X is alkoxy or halogen atom andm is 1 to 3. Texas Alkyls Co. proposed a method for preparing a complex[MgR₂ ]_(m) [AlR₃ ]_(n) by using AlR₃ in the above-mentioned system(Japanese Patent Application laid-open No. 18235/1973).

The present inventors have made strenuous studies on a method forpreparing an organomagnesium complex, and as a result found a novelmethod for producing an organomagnesium complex useful as a raw materialfor the catalyst employed in the production of Ziegler's processpolyolefins, and completed the present invention.

The present invention resides in:

a method for producing a hydrocarbon-soluble organomagnesium complex ofthe formula

Mg₆₀ Al.sub.β R¹ _(p) Y_(g)

wherein α, β, p and q each is a number greater than zero,

α/β = about 0.5 to 20,

2α and 3β = p + q,

q/β = about 0.5 to 1.5,

Y is OR² or OSiR³ R⁴ R⁵,

R¹, r² and R³ each independently is a hydrocarbon radical having 1 to 20carbon atoms, and

R⁴ and R⁵ each independently is a hydrocarbon radical having 1 to 20carbon atoms, hydrogen or a halogen atom,

which comprises reacting

(A) an organomagnesium compound of the formula

    R.sup.1.sub.a MgX.sub.2-a

with (B) an aluminum compound of the formula

AlYX₂

wherein

X is a halogen atom, and

a is a positive number up to 2.

The organomagnesium compound (A) identified by the general formula R¹_(a) MgX_(2-a), which is employed in the above-mentioned reaction, issynthesized from a halogenated hydrocarbon and metallic magnesiumaccording to a known method for preparing Grignard's reagents. Althougheither of ethers or inert hydrocarbons can be employed as the solventfor the synthesis, an ether not only reduces the yield of the objectiveorganomagnesium complex, but also is not a desirable component when theorganomagnesium complex is employed as a catalyst component. Accordinglyin the case of the synthesis thereof in ethers, it is desired to removeethers. Thus organomagnesium compounds synthesized in hydrocarbons areparticularly preferable.

The hydrocarbon group having 1-20 carbon atoms, expressed by R¹ in theabove-mentioned formula is an aliphatic, aromatic or alicyclichydrocarbon group, and among these, an aliphatic group is particularlypreferable. As for this group, for example, ethyl, propyl, butyl, amyl,hexyl, octyl, decyl and dodecyl are mentioned. As for the halogen atom,X Cl, Br or I can be employed, and Cl is preferable.

The aluminum compound (B) identified by the general formula AlYX₂ willbe described. As for the aluminum compound wherein Y is OR² in theformula AlYX₂, i.e. Al(OR²)X₂, the hydrocarbon group R² having 1-20carbon atoms is an aliphatic, aromatic or alicyclic hydrocarbon group,and among these, an aliphatic one such as propyl, butyl, amyl, etc. isparticularly preferable. As for the examples of these compounds, Al(OC₂H₅)Cl₂, Al(OC₃ H₇)Cl₂, Al(OC₄ H₉)Cl₂, Al(OC₅ H₁₁)Cl₂, Al(OC₆ H₁₃)Al₂,Al(OC₇ H₁₅)Cl₂, Al(OC₈ H₁₇)Cl₂, Al(OC₁₀ H₂₁)Cl₂, Al(OC₁₂ H₂₅)Cl₂, Al(OC₂H₅)Br₂, Al(OC₃ H₇)Br₂, Al(OC₄ H₉)Br₂, Al(OC₆ H₁₃)Br₂, Al(OC₈ H₁₇)Br₂,Al(OC₁₀ H₂₁)Br₂, Al(OC₂ H₅)I₂, Al(OC₃ H₇)I.sub. 2, Al(OC₄ H₉)I₂, Al(OC₆H₁₃)I₂, Al(OC₈ H₁₇)I₂, etc. are mentioned.

These compounds can be synthesized according to various methods, forexample, by the reaction of AlX₃ with Al(OR)₃, the reaction of AlCl₃,metallic Al and R² OH or the reaction of AlR² X₂ with O₂ R² OH.

As for the aluminum compound wherein Y is OSiR³ R⁴ R⁵ in formula AlYX₂,i.e. Al(OSiR³ R⁴ R⁵) X₂, R₃ is an aliphatic, aromatic or alicyclichydrocarbon group having 1-20 carbon atoms, and R₄ and R₅ eachindependently is an aliphatic, aromatic or alicyclic hydrocarbon grouphaving 1-20 carbon atoms, hydrogen or a halogen atom. Compounds whereinat least one of these groups is a hydrogen atom are particularlypreferable. As for the examples of these compounds, (H₂ CH₃ SiO)AlCl₂,[H(CH₃)₂ SiO]AlCl₂, (H.CH₃.C₂ H₅.SiO)AlCl₂, (H.C₄ H₉.C₆ H₅.SiO)AlCl₂,(H.CH₃.C₄ H₉.SiO)AlCl₂, (H.CH₃.nC₈ H₁₇.SiO)AlCl₂, [(C₂ H₅)₂.C₄H₉.SiO]AlCl₂, (H.C₂ H₅.C₆ H₁₃.SiO)AlCl₂, [(CH₃)₂.C₂ H₅.SiO]AlCl₂,[(Cl.(CH₃)₂.SiO]AlCl₂, (H₂.CH₃.SiO)AlBr₂, [H.(CH₃)₂.SiO]AlBr₂, (H.CH₃.C₂H₅.SiO)AlBr₂, (H₂ CH₃.SiO)AlI₂, [H.(CH₃)₂.SiO]AlI₂, (H.CH₃.C₂H₅.SiO)AlI₂, etc. are mentioned.

These aluminum compounds having a siloxy group can be synthesizedaccording to various methods, for example, by the reaction of analuminum compound of the formula AlR⁵ X₂ with a siloxane compound havinga structural unit of the formula ##STR1## or by the reaction of AlX₃with NaOSiR³ R⁴ R⁵.

The reaction of the organomagnesium compound (A) with the aluminumcompound (B) is carried out at a temperature of about 20°-200° C.,preferably about 50°-150° C., for about 0.5-20 hours. As for thereaction concentration of component (A) in carrying out this reaction, aconcentration range of about 0.1-2.5 mol/l may be employed, and in orderto obtain a solution of an organomagnesium complex in a highconcentration, it is advantageous to elevate the reaction concentrationof component (A) within a range wherein no obstacle occurs in operatingthe reaction. Component (B) may be employed in a concentration of about0.005-5 mol/l. The inert-hydrocarbon-medium-soluble organomagnesiumcomplex obtained by the reaction of (A) with (B) has a compositionwherein the molar ratio of Mg/Al is in the range of about 0.5-20. Thiscomposition can be optionally varied within this range by varying theamount of component (B) to be added to component (A) in the reactionsystem. As for the reaction medium used in carrying out the reaction of(A) with (B), aliphatic hydrocarbons such as hexane, heptane, etc.,aromatic hydrocarbons such as benzene, toluene, xylene, etc. andalicyclic hydrocarbons such as cyclohexane, methylcyclohexane, etc. maybe employed.

The complex synthesized according to the above-mentioned reaction isobtained in the form of a hydrocarbon solution, and presumed to be asole complex or a mixture of plural kinds of complexes. The compositionof the complex can be given by subjecting the solution to analysis, andalso it is possible to determine the average composition by measuringthe molecular weight. The substituent groups in the complex aredistributed to aluminum and magnesium atoms, and an exchange occursbetween the substituent groups. This fact is presumed from theappearance of new absorption of NMR spectra and the broadening of theabsorption. The ratio of Mg to Al, α/β, is important for obtaining thesoluble complex, and a range of about 0.5-20, particularly about 1-10,is preferable for obtaining a stable complex.

The specific features, effectivenesses and superiority to the known art,of the present invention will be hereinafter described in detail.

The first of the specific features of the present invention consists inthat the method of the present invention is superior in the points ofease of reaction, high reaction efficiency and safety as compared withknown methods. The second thereof consists in that the inerthydrocarbon-soluble complex obtained according to the method of thepresent invention is safe in storing and handling, and further when itis employed as an olefin polymerization catalyst, superioreffectivenesses are exhibited with respect to catalyst efficiency andcharacteristic properties of the resulting polymer.

With regard to the above-mentioned first specific feature, in the caseof the known art wherein AlCl₃ and Al(OR)₃ are employed, these compoundsare hardly soluble or insoluble in an inert hydrocarbon, whereas theAlYX₂ compounds of the present invention are readily soluble in saidsolvent and very easy to employ in reaction and handling. Further, themethod of the present invention provides a higher yield than knownmethods. This is apparent from the comparison of the data of thefollowing Table 1.

                                      Table I                                     __________________________________________________________________________    Experi-                                                                              Component                   Yield.sup.*2                               ment   (B)       Composition of complex.sup.*1                                                                   (%)                                        __________________________________________________________________________    Example                                                                       1      Al(OnC.sub.4 H.sub.9)Cl.sub.2                                                           MgAl.sub.0.30 (n-C.sub.4 H.sub.9).sub.2.60 (On-C.sub.4                        H.sub.9).sub.0.30 64                                         Compara-                                                                      tive   Al(On-C.sub.4 H.sub.9).sub.3                                                            MgAl.sub.0.29 (n-C.sub.4 H.sub.9).sub.2.23 (On-C.sub.4                        H.sub.9).sub.0.64 30                                         Ex.1                                                                          Compara-                                                                      tive   AlCl.sub.3                                                                              MgAl.sub.0.18 (n-C.sub.4 H.sub.9).sub.2.56                                                      14                                         Ex. 2                                                                         Compara-                                                                      tive   Al(On-C.sub.4 H.sub.9).sub.2 Cl                                                         MgAl.sub.0.41 (n-C.sub.4 H.sub.9).sub.2.43 (On-C.sub.4                        H.sub.9).sub.0.80 37                                         Ex. 3                                                                         __________________________________________________________________________     *.sup.1 As for the composition of complex, the solution was hydrolyzed an     Mg and Al were determined according to chelate titration method and           On-C.sub.4 H.sub.9 and n-C.sub.4 H.sub.9 were determined according to gas     chromatography method.                                                        *.sup.2 The yield means that of Mg contained in the solution, based upon      Mg(n-C.sub.4 H.sub.9).sub.2.                                             

As for the component (B) employed in Table 1, compounds other than thatof the present invention are all insoluble in the solvent. Further, whenAlCl₃ is employed as component (B) (see Comparative Example 2 mentionedbelow), the resulting complex contains no (On--C₄ H₉) group and isdifferent from that of the present invention.

As compared with known methods wherein an organoaluminum compound isemployed as the aluminum component, firstly the aluminum component ofthe present invention is much stabler to air and water than saidorganoaluminum component, and hence is very safe for transportation,storing and handling. Further, the methods for preparing the compoundsof known methods require synthesis of organoaluminum compounds orderivatives thereof, whereas the compounds of the present invention canbe very easily and cheaply synthesized from an aluminum halide, metallicaluminum and an alcohol (see Referential example 1 mentioned below).

The above-mentioned second specific feature of the present invention,i.e. superiority of product, will be hereinafter described.

The complexes obtained according to the method of the present inventioncontain OR² or OSiR³ R⁴ R⁵, and are milder in the reactivity than thosecontaining no such groups. Accordingly, they are safe for handling, andat the same time, when they are employed as a catalyst component, it ispossible to extend the range of catalyst preparation conditions, andthis fact is advantageous with respect of catalyst design.

In the case of the complex of the present invention wherein Y is OR²,the particle size of the resulting polymer can be made larger whilemaintaining the activity of the catalyst, there are no fine particlesand the apparent specific gravity can be made higher, as compared withthose of the prior art (see Example 35 and Comparative Examples 4 and 5mentioned below). In the case of the complex wherein Y is OSiR³ R⁴ R⁵,the groups participating in the reaction are so varied, e.g. Mg--R,Al--R and Si--H, and further, by changing the content of OSi group inaddition thereto, it becomes possible to control the molecular weightand molecular weight distribution of the resulting polymer, and hencethe complex is very useful. Further in the case of this complex, thereduction in activity due to the change of the amount of OSi is small,and a polymer having a sharp particle size distribution can be obtained(see Examples 36 and 37). The above-mentioned characteristic propertiesof catalyst are very important in the olefin polymerization process.

The method of the present invention will be further illusttrated indetail by way of the following non-limitative Examples.

EXAMPLE 1

Into a 200 ml capacity flask were introduced 0.05 mol of ethylaluminumdichloride and 50 ml of dried heptane under a nitrogen atmosphere. Thecontents were cooled with dry ice-methanol to -20° C., and then 50 ml ofdried heptane containing 0.05 mol of n-butyl alcohol was added theretowith stirring over 30 minutes. After completion of the addition, thetemperature was gradually returned to room temperature, and reaction wascontinued further for one hour to give a transparent solution, which wasfound, as the result of analysis, to be a solution of Al(On--Bu)Cl₂having a concentration of 0.5 ml/l.

Then, 3.8 g (0.16 gram atom) of magnesium powder was introduced into a500 ml capacity flask under a nitrogen atmosphere, and then thereto wasadded 30 ml taken from 200 ml of a dried heptane solution containing0.15 mol of n-butylchloride. The contents of the flask were heated withstirring up to their boiling point, and after the reaction started, theremaining n-butylchloride was added over 30 minutes. After completion ofthe addition, heating was continued further for one hour under reflux.

To the resulting reaction mixture was added 0.014 mol ofn-butoxyaluminum dichloride obtained in the above-mentioned reaction,together with 50 ml of heptane, and reaction was carried out at 80° C.for 3 hours. A solution containing magnesium in a concentration of 0.19mol/liter was obtained. As the result of analysis, the composition ofthe complex thus obtained was found to be MgAl₀.30 (n--C₄ H₉)₂.60(On--C₄ H₉)₀.30.

COMPARATIVE EXAMPLE 1

Reaction was carried out in the same manner as in Example 1, except thata heptane slurry of tri-n-butoxyaluminum was substituted forn-butoxyaluminum dichloride, to give a solution containing magnesium ina concentration of 0.09 mol/l. As the result of analysis, thecomposition of the complex thus obtained was

    MgAl.sub.0.29 (n--C.sub.4 H.sub.9).sub.2.23 (On--C.sub.4 H.sub.9).sub.0.64.

COMPARATIVE EXAMPLE 2

Reaction was carried out in the same manner as in Example 1, except thata heptane slurry of aluminum trichloride was substituted forn-butoxyaluminum dichloride, to give a solution containing magnesium ina concentration of 0.04 mol/l. As the result of analysis, thecomposition of the complex thus obtained was

    MgAl.sub.0.18 (n--C.sub.4 H.sub.9).sub.2.56.

COMPARATIVE EXAMPLE 3

Reaction was carried out in the same manner as in Example 1, except thata heptane slurry of di-n-butoxyaluminum monochloride was substituted forn-butoxyaluminum dichloride, to give a solution containing magnesium ina concentration of 0.11 mol/l. As the result of analysis, thecomposition of the complex thus obtained was found to be

    MgAl.sub.0.41 (n--C.sub.4 H.sub.9).sub.2.43 (On--C.sub.4 H.sub.9).sub.0.80.

EXAMPLES 2-8

(A) an organomagnesium compound prepared from magnesium powder and analkylhalide in the same manner as in Example 1, was reacted with analuminum compound under the conditions shown in Table 2. The results areshown in Table 2.

                                      Table 2                                     __________________________________________________________________________                               Complex                                                Magnesium                                                                             Aluminum  Temper-                                                                            Concen-                                                compound                                                                              compound  ature                                                                              tration                                            Ex. (A)     (B)       (° C) ×                                                               of Mg                                              No. (mol)   (mol)     time(hr)                                                                           mol/l                                                                              Composition of complex                        __________________________________________________________________________    2   n-C.sub.4 H.sub.9 MgCl                                                                (n-C.sub.8 H.sub.17 0)AlCl.sub.2                                                         80 × 3                                                                      0.20 MgAl.sub.0.17 (n-C.sub.4 H.sub.9).sub.2.34                                     (On-C.sub.8 H.sub.17).sub.0.16                   (0.15)  (0.013)                                                           3   n-C.sub.4 H.sub.9 MgBr                                                                (isoC.sub.5 H.sub.11 O)AlCl.sub.2                                                       80 × 3                                                                       0.14 MgAl.sub.0.40 (n-C.sub.4 H.sub.9).sub.2.81                                     (Oiso-C.sub.5 H.sub.11).sub.0.39                 (0.15)  (0.014)                                                           4   C.sub.2 H.sub.5 MgBr                                                                  (n-C.sub.4 H.sub.9 O)AlCl.sub.2                                                         80 × 3                                                                       0.16 MgAl.sub.0.28 (C.sub.2 H.sub.5).sub.2.57                                      (On-C.sub.4 H.sub.9).sub.0.27                     (0.15)  (0.011)                                                           5   n-C.sub.3 H.sub.7 MgI                                                                 (isoC.sub.4 H.sub.9 O)AlCl.sub.2                                                        80 × 3                                                                       0.18 MgAl.sub.0.56 (n-C.sub.3 H.sub.7).sub.3.11                                     (OisoC.sub.4 H.sub.9).sub.0.56                   (0.15)  (0.025)                                                           6   isoC.sub.3 H.sub.7 MgCl                                                               (n-C.sub.5 H.sub.11 O)AlCl.sub.2                                                        80 × 5                                                                       0.13 MgAl.sub.0.38 (isoC.sub.3 H.sub.7).sub.2.7                                    4 (On-C.sub.5 H.sub.11).sub.0.38                  (0.15)  (0.012)                                                           7   isoC.sub.4 H.sub.9 MgBr                                                               (isoC.sub.3 H.sub.7 O)AlCl.sub.2                                                        90 × 3                                                                       0.15 MgAl.sub.0.26 (isoC.sub.4 H.sub.9).sub.2.5                                    1 (OisoC.sub.3 H.sub.7).sub.0.25                  (0.15)  (0.010)                                                           8   n-C.sub.8 H.sub.17 MgCl                                                               (n-C.sub.5 H.sub.11 O)AlCl.sub.2                                                        90 × 3                                                                       0.30 MgAl.sub.0.11 (n-C.sub.8 H.sub.17).sub.2.2                                    2 (On-C.sub.5 H.sub.11).sub.0.12                  (0.20)  (0.009)                                                           __________________________________________________________________________

EXAMPLES 9-12

As shown in Table 3, (A) a dialkylmagnesium was reacted with (B) analuminum compound, in 250 ml of heptane, at 80° C., for 3 hours. Theresults are shown in Table 3.

                                      Table 3                                     __________________________________________________________________________                               Complex                                                Magnesium                                                                             Aluminum  Temper-                                                                            Concen-                                                compound                                                                              compound  ature                                                                              tration                                            Ex. (A)     (B)       (° C) ×                                                               of Mg                                              No. (mol)   (mol)     time (hr)                                                                          mol/l                                                                              Composition of complex                        __________________________________________________________________________    9   (C.sub.2 H.sub.5).sub.2 Mg                                                            (isoC.sub.5 H.sub.11 O)AlCl.sub.2                                                        90 × 4                                                                      0.20 MgAl.sub.0.31 (C.sub.2 H.sub.5).sub.2.61                                      (OisoC.sub.5 H.sub.11).sub.0.30                   (0.10)  (0.016)                                                           10  (n-C.sub.4 H.sub.9).sub.2 Mg                                                          (n-C.sub.4 H.sub.9 O)AlCl.sub.2                                                         80 × 3                                                                       0.22 MgAl.sub.0.24 (n-C.sub.4 H.sub.9).sub.2.48                                     (OC.sub.4 H.sub.9).sub.0.24                      (0.08)  (0.013)                                                           11  (n-C.sub.6 H.sub.13).sub.2 Mg                                                         (n-C.sub.8 H.sub.17 O)AlCl.sub.2                                                        80 × 3                                                                       0.19 MgAl.sub.0.15 (n-C.sub.6 H.sub.13).sub.2.3                                    1 (O-nC.sub.8 H.sub.17).sub.0.14                  (0.08)  (0.007)                                                           12  (C.sub.6 H.sub.5).sub.2 Mg                                                            (n-C.sub.3 H.sub.7 O)AlCl.sub.2                                                         80 × 3                                                                       0.14 MgAl.sub.0.38 (C.sub.6 H.sub.5).sub.2.74                                      (O-nC.sub.3 H.sub.7).sub.0.39                     (0.08)  (0.025)                                                           __________________________________________________________________________

EXAMPLE 13

Into a 200 ml capacity flask were introduced 16 g (0.06 mol) of aluminumtribromide, 7.4 g (0.03 mol) of tri-n-butoxyaluminum and 90 ml of driedheptane under a nitrogen atmosphere. Reaction was carried out at 98° C.for 5 hours. Solid components completely dissolved to give a transparentsolution, which was found, as the result of analysis, to be a solutionof Al(On--Bu)Br₂ in a concentration of 1 M/l.

Then, 7.6 g (0.32 gram atom) of magnesium powder was introduced into a500 ml capacity flask under a nitrogen atmosphere, and then thereto wasadded 30 ml taken from 200 ml of a dried heptane solution containing0.30 mol of n-butylchloride. The contents of the flask were heated withstirring up to their boiling point. Since the reaction started, theremaining n-butylchloride was added over 30 minutes. After completion ofthe addition, heating was carried out for another one hour under reflux.

To the resulting reaction mixture were added 0.010 mol ofn-butoxyaluminum dibromide obtained in the above-mentioned reaction,together with 50 ml of heptane. Reaction was carried out at 80° C. for 3hours to give a solution containing magnesium in a concentration of 0.35mol/l. As the result of analysis, the composition of the complex thusobtained was found to be

    MgAl.sub.0.13 (n--C.sub.4 H.sub.9).sub.2.25 (On--C.sub.4 H.sub.9).sub.0.16.

EXAMPLES 14-22

(A) an organomagnesium compound prepared from magnesium powder and analkylhalide in the same manner as in Example 1, was reacted with (B) analuminum compound under the conditions shown in Table 4. The results areshown in Table 4.

                                      Table 4                                     __________________________________________________________________________                             Complex                                                  Magnesium                                                                            Aluminum Temper-                                                                            Concen-                                                  compound                                                                             compound ature                                                                              tration                                              Ex. (A)    (B)      (° C) ×                                                               of Mg                                                No. (mol)  (mol)    time(hr)                                                                           mol/l                                                                              Composition of complex                          __________________________________________________________________________    14  n-C.sub.4 H.sub.9 MgCl                                                               (n-C.sub.8 H.sub.17 0)AlBr.sub.2                                                       98 × 3                                                                       0.17 MgAl.sub.0.17 (n-C.sub.4 H.sub.9).sub.2.34                                    (O n-C.sub.8 H.sub.17).sub.0.16                     (0.15) (0.008)                                                            15  n-C.sub.3 H.sub.7 MgBr                                                               (n-C.sub.3 H.sub.7 O)AlI.sub.2                                                         98 × 2                                                                       0.23 MgAl.sub.0.38 (n-C.sub.3 H.sub.7).sub.2.75                                    (O n-C.sub.3 H.sub.7).sub.0.39                      (0.20) (0.016)                                                            16  n-C.sub.5 H.sub.11 MgBr                                                              (n-C.sub.4 H.sub.9 O)AlI.sub.2                                                         60 × 5                                                                       0.45 MgAl.sub.0.19 (n-C.sub.5 H.sub.11).sub.2.36                                   (O n-C.sub.4 H.sub.9).sub.0.19                      (0.40) (0.021)                                                            17  n-C.sub.4 H.sub.9 MgBr                                                               (iso-C.sub.3 H.sub.7 O)AlI.sub.2                                                       60 × 5                                                                       0.60 MgAl.sub.0.49 (n-C.sub.4 H.sub.9).sub.2.99                                    (OisoC.sub.3 H.sub.7).sub.0.48                      (0.45) (0.075)                                                            18  n-C.sub.6 H.sub.13 MgCl                                                              (n-C.sub.5 H.sub.11 O)AlBr.sub.2                                                       60 ×  8                                                                      0.38 MgAl.sub.0.26 (n-C.sub.6 H.sub.13).sub.2.54                                   (O n-C.sub.5 H.sub.11).sub.0.23                     0.30   (0.024)                                                            19  n-C.sub.8 H.sub.17 MgCl                                                              (iso-C.sub.3 H.sub.7 O)AlBr.sub.2                                                      98 × 1                                                                       0.42 MgAl.sub.0.35 (n-C.sub.8 H.sub.17).sub.2.72                                   (OisoC.sub.3 H.sub.7).sub.0.35                      0.30   (0.037)                                                            20  C.sub.2 H.sub.5 MgCl                                                                 (isoC.sub.4 H.sub.9 O)AlBr.sub.2                                                       98 × 3                                                                       0.11 MgAl.sub.0.12 (C.sub.2 H.sub.5).sub.2.21                                      (OisoC.sub.4 H.sub.9).sub.0.14                      0.15   (0.005)                                                            21  iso-C.sub.3 H.sub.7 MgI                                                              (n-C.sub.8 H.sub.17 O)AlI.sub.2                                                        98 × 3                                                                       0.34 MgAl.sub.0.43 (iso-C.sub.3 H.sub.7).sub.2.87                                   (O n-C.sub.8 H.sub.17).sub.0.42                    (0.40) (0.037)                                                            22  iso-C.sub.4 H.sub.9 MgI                                                              (C.sub.6 H.sub.5 O)AlBr.sub.2                                                          98 × 8                                                                       0.26 MgAl.sub.0.37 (iso-C.sub.4 H.sub.9).sub.2.74                                   (OC.sub.6 H.sub.5).sub.0.36                        (0.40) (0.024)                                                            __________________________________________________________________________

EXAMPLE 23

Into a 200 ml flask were introduced 0.05 mol of ethylaluminum dichlorideand 50 ml of dried heptane, under a nitrogen atmosphere, and then wasadded 50 ml of a dried heptane solution containing 0.05 mol ofpolyhydromethylsiloxane. Reaction was carried out under reflux byheating for 3 hours. The resulting reaction solution was found, as theresult of analysis, to be a solution of (H.CH₃.C₂ H₅ SiO)AlCl₂ having aconcentration of 0.5 mol/l.

Then, 3.8 g (0.16 gram atom) of magnesium powder was introduced into a500 ml flask under a nitrogen atmosphere and then thereto was added 30ml taken from 200 ml of a dried heptane solution containing 0.15 mol ofn-butylchloride. Stirring was carried out under reflux by heating. Oncethe reaction started, the remaining solution of n-butylchloride wasadded over 30 minutes. After completion of the addition, heating wascontinued further for one hour under reflux.

To the resulting reaction mixture were added 0.009 mol of (H.CH₃.C₂ H₅SiO)AlCl₂ obtained in the above-mentioned reaction, together with 50 mlof heptane. Reaction was carried out at 98° C. for 3 hours to give asolution containing magnesium in a concentration of 0.13 mol/l. As theresult of analysis, the composition of the complex thus obtained wasfound to be

    MgAl.sub.0.29 (n--C.sub.4 H.sub.9).sub.2.59 (OSiH.CH.sub.3.C.sub.2 H.sub.5).sub.0.28.

EXAMPLES 24-31

Various kinds of magnesium compounds and aluminum compounds prepared inthe same manner as in Example 23 were reacted together in 250 ml ofheptane under the conditions shown in Table 5. The results are shown inTable 5.

                                      Table 5                                     __________________________________________________________________________                                     Complex                                                                  Temper-                                                                            Concen-                                           Magnesium                                                                             Aluminum       ature                                                                              tration                                      Ex.  compound                                                                              compound       (° C) ×                                                               of Mg                                        No.  (mol)   (mol)          time(hr)                                                                           (mol/l)                                                                            Composition of complex                  __________________________________________________________________________    24   n-C.sub.8 H.sub.17 MgCl                                                               (H . CH.sub.3 . C.sub.2 H.sub.5 SiO)AlCl.sub.2                                               80 × 3                                                                       0.21 MgAl.sub.0.17 (n-C.sub.8 H.sub.17).s                                          ub.2.32 (OSi . H . CH.sub.3 .                                                 C.sub.2 H.sub.5).sub.0.17                    (0.15)  (0.009)                                                          25   n-C.sub.10 H.sub.21 MgCl                                                              (H . CH.sub.3 . n-C.sub.4 H.sub.9 SiO)AlBr.sub.2                                             98 × 2                                                                       0.22 MgAl.sub.0.18 (n-C.sub.10 H.sub.21).                                          sub.2.34 (OSiH . CH.sub.3 .                                                   n-C.sub.4 H.sub.9).sub.0.18                  (0.15)  (0.020)                                                          26   n-C.sub.3 H.sub.7 MgCl                                                                (H . CH.sub.3 . C.sub.6 H.sub.5 SiO)AlI.sub.2                                                98 × 3                                                                       0.15 MgAl.sub.0.37 (n-C.sub.3 H.sub.7).su                                          b.2.74 (OSiH . CH.sub.3 . C.sub.6                                             H.sub.5).sub.0.36                            (0.15)  (0.013)                                                          27   n-C.sub.4 H.sub.9 MgCl                                                                [(CH.sub.3).sub.2  . n-C.sub.4 H.sub.9 SiO]AlCl.sub.2                                        98 × 3                                                                       0.16 MgAl.sub.0.30 (n-C.sub.4 H.sub.9).su                                          b.2.61 [OSi(CH.sub.3).sub.2 .                                                 n-C.sub.4 H.sub.9 ].sub.0.30                 (0.15)  (0.012)                                                          28   n-C.sub.4 H.sub.9 MgCl                                                                (H.sub.2 CH.sub.3 SiO)AlCl.sub.2                                                             70 × 5                                                                       0.44 MgAl.sub.0.19 (n-C.sub.4 H.sub.9).su                                          b.2.36 (OSiH.sub.2 .                                                          CH.sub.3).sub.0.20                           (0.23)  (0.021)                                                          29   iso-C.sub.4 H.sub.9 MgCl                                                              [H . (CH.sub.3).sub.2 SiO]AlCl.sub.2                                                          98 × 10                                                                     0.20 MgAl.sub.0.39 (iso-C.sub.4 H.sub.9).                                          sub.2.78 [Osi(CH.sub.3).sub.2                                                 H].sub.0.38                                  (0.25)  (0.018)                                                          30   n-C.sub.4 H.sub.9 MgBr                                                                (H . CH.sub.3 . iso-C.sub.4 H.sub.9 SiO)AlCl.sub.2                                           98 × 6                                                                       0.14 MgAl.sub.0.58 (n-C.sub.4 H.sub.9).su                                          b.3.15 (OSiH . CH.sub.3 .                                                     iso-C.sub.4 H.sub.9).sub.0.57                (0.15)  (0.020)                                                          31   C.sub.2 H.sub.5 MgI                                                                   [H . (C.sub.2 H.sub.5).sub.2 SiO]AlCl.sub.2                                                  98 × 5                                                                       0.15 MgAl.sub.0.47 (C.sub.2 H.sub.5).sub.                                          2.95 [OSiH . (C.sub.2 H.sub.5).sub.                                           2 ].sub.0.48                                 (0.15)  (0.018)                                                          __________________________________________________________________________

EXAMPLES 32-34

Various kinds of dialkylmagnesiums and aluminum compounds shown in Table6 were reacted together in 250 ml of heptane under the conditions shownin Table 6. The results are shown in Table 6.

                                      Table 6                                     __________________________________________________________________________                                   Complex                                                                  Temper-                                                                            Concen-                                            Magnesium                                                                            Aluminum       ature                                                                              tration                                        Ex. compound                                                                             compound       (° C) ×                                                               of Mg                                          No. (mol)  (mol)          time(hr)                                                                           (mol/l)                                                                            Composition of complex                    __________________________________________________________________________    32  (n-C.sub.4 H.sub.9).sub.2 Mg                                                         (H . C.sub.2 H.sub.5 . C.sub.6 H.sub.5 SiO)AlCl.sub.2                                        80 × 1                                                                       0.19 MgAl.sub.0.28 (n-C.sub.4 H.sub.9).sub.                                        2.55 (OSiH . C.sub.2 H.sub.5 .                                                C.sub.6 H.sub.5).sub.0.27                     (0.08) (0.013)                                                            33  (C.sub.2 H.sub.5).sub.2 Mg                                                           (H . C.sub.2 H.sub.5 . n-C.sub.4 H.sub.9 SiO)AlBr.sub.2                                      98 × 4                                                                       0.17 MgAl.sub.0.34 (C.sub.2 H.sub.5).sub.2.                                        68 (OSiH C.sub.2 H.sub.5 . n-C.sub.4                                          H.sub.9).sub.0.36                             (0.08) (0.014)                                                            34  (n-C.sub.6 H.sub.13).sub.2 Mg                                                        [H . C.sub.2 H.sub.5 . C.sub.6 H.sub.5 SiO]AlCl.sub.2                                        98 × 10                                                                      0.43 MgAl.sub.0.24 (n-C.sub.6 H.sub.13).sub                                        .2.45 [OSiH . C.sub.2 H.sub.5 .                                               C.sub. 6 H.sub.5 ].sub.0.26                   (0.15) (0.026)                                                            __________________________________________________________________________

EXAMPLES 35-37 AND COMPARATIVE EXAMPLES 4 and 5

In these Examples and Comparative Examples, catalyst preparation andpolymerization were carried out in order to show the usefulness of thecomplexes of the present invention for an ethylene polymerizationcatalyst.

(1) Preparation of solid catalyst

1.2 l of dried hexane was introduced into a 4 l capacity reactorequipped with a stirrer the inside of which reactor had been dried invacuo and purged with nitrogen, and the hexane was kept at 0° C. withstirring. Two dropping funnels were connected to this reactor. 600 ml ofa hexane solution of titanium tetrachloride in a connection of 1.0 mol/lwas introduced into one of the funnels and 600 ml of a complex solution(adjusted to a concentration of 1.0 mol/l in hexane) shown in Table 7was introduced into the other funnel. The two components were droppedfrom the funnels, with stirring at 0° C. over 3 hours. Further, stirringwas continued at this temperature for one hour to effect reaction. Theresulting solid component was isolated and dried.

(2) Polymerization

800 ml of heptane was introduced into a 1.5 l capacity autoclave theinside of which had been purged with nitrogen. While maintaining thetemperature at 85° C., 2.0 Kg/cm² of hydrogen and 2.0 Kg/cm² of ethylenewere pressurized into the autoclave to raise the total pressure to 4.0Kg/cm². Ten mg of the solid component obtained in step (1) and 0.4 mmolof triisobutylaluminum were added to the autoclave. Polymerization wascarried out for 30 minutes, while supplying ethylene. The results areshown in Table 7.

    Table 7      Results of polymerization    Particle size distribution Complex  Bulk     of polymer particles  mesh %  Preparation  Yield Density  20- 35- 48-     100- 145-  Ex. method  Composition (g) (g/cc) <20 35 48 100 145 200     >200    Al(On-C.sub.4 H.sub.9)Cl.sub.2            35 of Example 1     MgAl.sub.0.22 (n-C.sub.4 H.sub.9).sub.2.44 (On-C.sub.4 H.sub.9).sub.0.25     215 0.41 0 13  45  28 14 0 0  was used.  (H . CH.sub.3 . C.sub.2 H.sub.5     SiO)-  36 AlCl.sub.2 of Example MgAl.sub.0.32 (n-C.sub.4      H.sub.9).sub.2.66 (OSi . H . CH.sub.3 . C.sub.2 H.sub.5) 198 0.37 0 0 5     12 75 8 0  23 was used 0.33  37   " MgAl.sub.0.72 (n-C.sub.4      H.sub.9).sub.3.31 (OSi . H . CH.sub.3 . C.sub.2 H.sub.5) 182 0.39 0 0 6     19 69 6 0   0.85 Compara- Al(On-C.sub.4      H.sub.9).sub.3 tive of Comparative MgAl.sub.0.32 (n-C.sub.4      H.sub.9).sub.2.06 (On-C.sub.4 H.sub.9).sub.0.85 142 0.28 5 9 16  22 25     13  10  Ex. 4 Ex. 1 was used. Compara- AlCl.sub.3 of Compara- tive tive     Ex. 2 was MgAl.sub.0.30 (n-C.sub.4 H.sub.9).sub.2.88 165 0.30 18  5 7 17     20 15  18       Ex. 5 used.

REFERENTIAL EXAMPLE 1

Into a 200 ml capacity flask were introduced 8.0 g (0.06 mol) ofaluminum trichloride, 0.81 g (0.03 mol) of aluminum powder and 2.2 g(0.030 mol) of n-butanol, together with 90 ml of dried hexane, under anitrogen atmosphere. A reflux condenser was attached to the flask, andreaction was carried out for 2 hours at the reflux temperature of thecontents. Aluminum trichloride and aluminum powder both of which wereinitially insoluble, reacted to give a uniform solution. This solutionwas found, as the result of analysis, to be a solution of Al(On--C₄H₉)Cl₂ having a concentration of 1.1 mol/l.

It will be appreciated that the instant specification and claims are setforth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. A method for producing a hydrocarbon-solubleorganomagnesium complex of the formula

    Mg.sub.α Al.sub.β R.sup.1.sub.p Y.sub.q

wherein α, β, p and q each is a number greater than zero, α/β = about0.5 to 20, α and 3β = p + q, q/β = about 0.5 to 1.5, Y is OR² or OSiR³R⁴ R⁵, R¹, r² and R³ each independently is a hydrocarbon radical having1 to 20 carbon atoms, and R⁴ and R⁵ each independently is a hydrocarbonradical having 1 to 20 carbon atoms, hydrogen or a halogen atom, whichcomprises reacting in an inert hydrocarbon medium at a temperature ofabout 50°-150° C. and for about 0.5 to 20 hours (A) an ether-freesolution containing about 0.1-2.5 mols per liter of organomagnesiumcompound of the formula

    R.sup.1.sub.a MgX.sub.2-a

with (B) a solution containing about 0.005-5 mols per liter of analuminum compound of the formula

    AlYX.sub.2

wherein X is a halogen atom, and a is a positive number up to
 2. 2. Themethod according to claim 1,wherein α/β = about 1 to 10, at least one ofR⁴ and R⁵ is hydrogen, and X is chlorine.
 3. The method according toclaim 1 wherein R¹ is an aliphatic hydrocarbon group.
 4. The methodaccording to claim 1 wherein Y is OR².
 5. The method according to claim3 wherein Y is OR².
 6. The method according to claim 4 wherein R² ispropyl, butyl or amyl.
 7. The method according to claim 1 wherein Y isOSiR³ R⁴ R⁵.
 8. The method according to claim 7 wherein at least one ofR⁴ and R⁵ is a hydrogen atom.
 9. The method according to claim 3 whereinY is OSiR³ R⁴ R⁵.
 10. The method according to claim 9 wherein at leastone of R⁴ and R⁵ is a hydrogen atom.